Oxidation of silver metal and silver(I) cations by molybdenum, tungsten, and uranium hexafluorides and by the nitrosonium cation in acetonitrile. Preparation and properties of silver(III) hexafluorometalates(V)

Abstract

Silver metal is oxidized by molybdenum, tungsten, or uranium hexafluorides or by the nitrosonium cation, all in acetonitrile, to give the solvated silver(I) cation from which silver(I) cations with ligated pyridine, py, or trimethyl phosphite are readily prepared. Oxidation of [Ag(py)₄][MoF₆] and [Ag(py)₂][UF₆] in MeCN by MoF₆ and UF₆respectively leads to the silver(III) compounds [Ag(py)₄(NCMe)][MoF₆]₃ and [Ag(py)₂(NCMe)₃][UF₆]₃. The cations are strong oxidizing agents in MeCN. The solvated copper(I) cation and molecular iodine are oxidized to give copper(II) and the [I(NCMe)₂]⁺ cation.